EP2227320B1 - Mélanges d'huile végétale modifiée par copolymère séquencé, et de polymère et procédés de réalisation de ceux-ci - Google Patents

Mélanges d'huile végétale modifiée par copolymère séquencé, et de polymère et procédés de réalisation de ceux-ci Download PDF

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Publication number
EP2227320B1
EP2227320B1 EP08861655A EP08861655A EP2227320B1 EP 2227320 B1 EP2227320 B1 EP 2227320B1 EP 08861655 A EP08861655 A EP 08861655A EP 08861655 A EP08861655 A EP 08861655A EP 2227320 B1 EP2227320 B1 EP 2227320B1
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EP
European Patent Office
Prior art keywords
polylactide
vegetable oil
block copolymer
composition
homopolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP08861655A
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German (de)
English (en)
Other versions
EP2227320A4 (fr
EP2227320A1 (fr
Inventor
Eric John Connell
Marc Andrew Hillmyer
Kwanho Chang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Engineering and Manufacturing North America Inc
University of Minnesota
Original Assignee
Toyota Motor Engineering and Manufacturing North America Inc
University of Minnesota
Toyota Engineering and Manufacturing North America Inc
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Application filed by Toyota Motor Engineering and Manufacturing North America Inc, University of Minnesota, Toyota Engineering and Manufacturing North America Inc filed Critical Toyota Motor Engineering and Manufacturing North America Inc
Publication of EP2227320A1 publication Critical patent/EP2227320A1/fr
Publication of EP2227320A4 publication Critical patent/EP2227320A4/fr
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Publication of EP2227320B1 publication Critical patent/EP2227320B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention is generally related to biodegradable blends of low molecular weight oils and high molecular weight polymers, and is specifically related to vegetable oils dispersed in a matrix of the aliphatic polyesters, wherein the dispersion is aided by a block copolymer.
  • aliphatic polyesters such as polylactide materials, which are attractive polymer materials, because of their stiffness and tensile strength.
  • Aliphatic polyesters may be used for disposable or durable molded resin applications.
  • US 200310049320 describes a composition for providing an in-situ forming controlled release microcarrier delivery system, the composition being a gelled, syringeable droplet-in-oil dispersion comprising a biocompatible, biodegradeable or non-biodegradeable polymer in a water-soluble organic solvent and a pharmaceutically acceptable biocompatible emulsifier in solution in a biocompatible oil.
  • US 5,756,651 describes a degradeable film having a high impact resistance comprising (a) at least about 50% by weight of a crystalline polylactide as the primary polymer; (b) a degradeable impact modifier; and (c) a degradeable plasticizer having a weight average molecular weight of no more than about 2,000 daltons.
  • the invention provides a polymer and vegetable oil based composition
  • a polylactide homopolymer comprising: a polylactide homopolymer, a vegetable oil and a block copolymer, wherein:
  • the invention also relates to a method of inverting the phases in a polymer and vegetable oil based emulsion comprising: providing a polylactide homopolymer composition, a vegetable composition and a polyisoprene-polylactide block copolymer in a mixing vessel; mixing the polylactide homopolymer, the vegetable oil, and the polyisoprene-polylactide block copolymer to produce a first emulsion comprising vegetable oil dispersed within the polylactide homopolymer and reducing the volume fraction of the polylactide inside the polyisoprene-polylactide block copolymer below 70% to produce a second emulsion, wherein the polylactide homopolymer is dispersed within the vegetable oil.
  • a polymer and vegetable oil based composition for example, an emulsion (or a stabilized dispersion of one phase in another) is provided.
  • the composition comprises a polylactide homopolymer, a vegetable oil dispersed inside the polylactide homopolymer, and a block copolymer configured to aid the dispersion of the vegetable oil inside the polylactide homopolymer.
  • polylactide and vegetable oil based composition is provided but with polylactide and vegetable oil phases inverted.
  • This inverted phase composition comprises a vegetable oil, a polylactide homopolymer, and a polyisoprene-polylactide block copolymer containing less than 70% by volume polylactide.
  • a method of achieving inverted phases in a polymer and vegetable oil based emulsion comprises the steps of providing a polylactide homopolymer composition, a vegetable oil composition, and a block copolymer in a mixing vessel, and mixing these components to produce a first emulsion comprising vegetable oil dispersed within the polylactide homopolymer.
  • the method further comprises reducing the volume fraction of the polylactide in the block copolymer to below 70% in a separate blend.
  • the second emulsion comprises polylactide homopolymer dispersed within the vegetable oil.
  • FIG. 1 is a graphical illustration showing the effect of the volume fraction of the polylactide in the polyisoprene-polylactide block copolymer on the blends of the present invention according to one or more embodiments of the present invention.
  • Embodiments of the present invention are directed to a polymer and vegetable oil based composition.
  • the “composition” may include and may be described by various structural names, e.g. micelles, emulsions, colloids, lamellar structures, blends, or combinations thereof.
  • the composition comprises a polylactide homopolymer and a vegetable oil dispersed inside the polylactide homopolymer.
  • the polymer e.g. polylactide
  • the inventors utilized a block copolymer configured to aid the dispersion of the vegetable oil inside the polylactide homopolymer.
  • the vegetable oil may be dispersed as droplets within a matrix defined by the polylactide homopolymer.
  • Further embodiments of the present invention are directed to an inverted polymer and vegetable oil based composition
  • the polylactide homopolymer may comprise many polymers suitable for use in a biorenewable blend, (e.g. poly(L-lactide) (PLLA), its stereoisomers, or combinations thereof).
  • PLLA poly(L-lactide)
  • the PLLA may be produced through various methods familiar to one of ordinary skill in the art, for example, ring opening polymerization of L-lactide.
  • the vegetable oil may also comprise numerous suitable components.
  • a vegetable oil is a mixture of triglycerides with a varying degree of unsaturated fatty acids.
  • soybean oil may be utilized in a modified or unmodified form.
  • the block copolymer may comprise any polymer composition (e.g., a surfactant) suitable to address the above described immiscibility issues and aid in the dispersion of vegetable oil inside a polylactide homopolymer matrix.
  • the block copolymer comprises various properties optimized for the present dispersion, for example, block copolymers with substantially symmetric compositions and a molecular weights of the polyisoprene blocks between 5,900-24,000 daltons.
  • the block copolymer comprises a polyisoprene-polylactide block copolymer, such as poly(isoprene-b-lactide) (ILLA).
  • the PLLA/SOY/ILLA blend includes tensile modulus of 450 MPa, a tensile strength of 30 MPa, and an ultimate elongation of 60% in the presence of 10% SOY by weight.
  • a block copolymer modified blend may support a larger percentage of vegetable oil in the dispersion.
  • the composition may comprise 0.1 % to 5% by wt. of the block copolymer (e.g., ILLA), 5% to 20% by wt. of the vegetable oil composition (e.g., soybean oil), and 70% to 90% by wt. of the polylactide (e.g...PLLA).
  • the block copolymer may control the phase inversion behavior of the blends,or stabilize a blend after phase inversion.
  • the volume fraction of the PLLA or the volume fraction of the SOY must be controlled to ensure the soybean oil droplets are dispersed within the PLLA matrix.
  • the soybean oil droplets may be exuded from the dispersion and become converted into a continuous phrase.
  • the phases of the polymer and vegetable oil based composition may be inverted by lowering the volume fraction of polylactide in the block copolymer. This may occur, in one embodiment, when the polylactide defines a volume fraction f PLLA less than 70% in the ILLA block copolymer.
  • This phase inversion may also be controlled by altering the processing conditions involved in producing the blend.
  • asymmetric block copolymers with f PLLA 0.7 favor disordered spherical inclusions which are dispersed as isolated objects, but can aggregate into other large domains.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Colloid Chemistry (AREA)

Claims (14)

  1. Composition à base de polymère et d'huile végétale, qui comprend un homopolymère polylactide, une huile végétale et un copolymère à blocs et dans laquelle :
    i) l'huile végétale est dispersée au sein de l'homopolymère polylactide, et le copolymère à blocs est conçu pour favoriser la dispersion de l'huile végétale au sein de l'homopolymère polylactide, lequel copolymère à blocs est un copolymère à blocs polyisoprène-polylactide ;
    ii) ou bien au moins une partie du polylactide est dispersée au sein de l'huile végétale, et le copolymère à blocs est un copolymère à blocs polyisoprène-polylactide comportant au moins 70 % en volume de polylactide, lequel copolymère à blocs est conçu pour stabiliser la dispersion du polylactide au sein de l'huile végétale.
  2. Composition conforme à la revendication 1, dans laquelle l'homopolymère polylactide comprend du poly(L-lactide), ses stéréoisomères, ou leurs combinaisons.
  3. Composition conforme à la revendication 1, dans laquelle l'huile végétale comprend de l'huile de soja.
  4. Composition conforme à la revendication 1, dans laquelle le copolymère à blocs comprend un poly(isoprène-bloc-lactide).
  5. Composition conforme à la revendication 1, item (i), dans laquelle le copolymère à blocs est un tensioactif sensiblement symétrique.
  6. Composition conforme à la revendication 1, item (i), dans laquelle le copolymère à blocs représente de 0,1 à 5 % du poids de la composition.
  7. Composition conforme à la revendication 1, item (i), dans laquelle l'huile végétale représente de 5 à 20 % du poids de la composition.
  8. Composition conforme à la revendication 1, item (i), dans laquelle le polylactide représente de 70 à 90 % du poids de la composition.
  9. Composition conforme à la revendication 1, item (i), dans laquelle l'huile végétale est dispersée, sous forme de gouttelettes, dans la matrice de polylactide.
  10. Composition conforme à la revendication 1, item (i), dans laquelle l'homopolymère polylactide comprend du poly(L-lactide), l'huile végétale comprend de l'huile de soja, et le copolymère à blocs comprend un poly(isoprène-bloc-lactide).
  11. Procédé de réalisation d'une inversion de phases dans une émulsion à base de polymère et d'huile végétale, lequel procédé comporte les étapes suivantes :
    i) mettre dans un récipient de mélangeage une composition d'homopolymère polylactide, une composition d'huile végétale et un copolymère à blocs polyisoprène-polylactide ;
    ii) mélanger l'homopolymère polylactide, l'huile végétale et le copolymère à blocs polyisoprène-polylactide, de manière à produire une première émulsion où l'huile végétale est dispersée au sein de l'homopolymère polylactide ;
    iii) et réduire à moins de 70 % la fraction en volume du polylactide au sein du copolymère à blocs polyisoprène-polylactide, de manière à produire une deuxième émulsion où l'homopolymère polylactide est dispersé au sein de l'huile végétale.
  12. Procédé conforme à la revendication 11, dans lequel l'homopolymère polylactide comprend du poly(L-lactide), ses stéréoisomères, ou leurs combinaisons.
  13. Procédé conforme à la revendication 11, dans lequel le copolymère à blocs est injecté à l'état de poudre dans le récipient de mélangeage, avant l'addition de l'huile végétale.
  14. Procédé conforme à la revendication 11, dans lequel l'huile végétale est ajoutée goutte à goutte.
EP08861655A 2007-12-17 2008-12-11 Mélanges d'huile végétale modifiée par copolymère séquencé, et de polymère et procédés de réalisation de ceux-ci Not-in-force EP2227320B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/957,559 US7888418B2 (en) 2007-12-17 2007-12-17 Block copolymer modified vegetable oil and polymer blends and methods of making same
PCT/US2008/086320 WO2009079313A1 (fr) 2007-12-17 2008-12-11 Mélanges d'huile végétale modifiée par copolymère séquencé, et de polymère et procédés de réalisation de ceux-ci

Publications (3)

Publication Number Publication Date
EP2227320A1 EP2227320A1 (fr) 2010-09-15
EP2227320A4 EP2227320A4 (fr) 2011-05-04
EP2227320B1 true EP2227320B1 (fr) 2012-08-29

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EP08861655A Not-in-force EP2227320B1 (fr) 2007-12-17 2008-12-11 Mélanges d'huile végétale modifiée par copolymère séquencé, et de polymère et procédés de réalisation de ceux-ci

Country Status (4)

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US (1) US7888418B2 (fr)
EP (1) EP2227320B1 (fr)
JP (1) JP4870839B2 (fr)
WO (1) WO2009079313A1 (fr)

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US20150005551A1 (en) * 2013-07-01 2015-01-01 Syntroleum Corporation Method of processing adulterated biomass feedstocks
KR102255307B1 (ko) 2014-11-05 2021-05-24 삼성전자주식회사 열가소성 수지 조성물 및 이로 이루어진 성형품
CN106280165B (zh) * 2016-08-31 2021-07-13 黑龙江省森林保护研究所 高分子阻火灭火凝胶及其制备方法

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Also Published As

Publication number Publication date
EP2227320A4 (fr) 2011-05-04
WO2009079313A1 (fr) 2009-06-25
EP2227320A1 (fr) 2010-09-15
JP2011506752A (ja) 2011-03-03
US7888418B2 (en) 2011-02-15
US20090156746A1 (en) 2009-06-18
JP4870839B2 (ja) 2012-02-08

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